Polyazo dyestuffs



' radicals such as In this formula AN=N- stands for the residue of adiazotized diamine of the benzene series, X stands for hydrogen or theSOaH-group and n for the values one or zero. I v

In comparison with the dyestuflfs known from Patented Mar. 26, 1940UNITEo; STATES roLYAzo nwEsTUFFs Theodor Kollmann, Leverkusen-Wiesdorf,Germany, assignorto General- Aniline & Corporation, ajcorporation ofDelaware No Drawing. Application September -21, 1938,

SerialNo; 231,015. 1937 The present invention relates to new substantivegreen polyazo dyestufis and to a method of preparing the same.

In U. S. Patent 1,150,656 substantive green polyazo dyestuffs aredescribe'dwhic'h arerenbenz 1.2-naphthimidazo1-5-hydroiqr '7 F- sunoniacid or m-aminobenz-1.2-naphthathiazole-5-hydroxy-l-sulfonic acid,diazotizing, coupling with resorcinol and saponifying or reducing. Underaminobenzoylated 2 amino-5-hydroxynaphthalene-7-sulfonic acids Iunderstand such derivatives of 2-amino-5-hydroxynaphthalene-7-sulfonicacid, in which one hydrogen atom of the amino group in the 2-position isreplaced by I CO.NH a

' HQN Very clear green cotton'dyestufis of excellent fastness propertiesare thus obtained. I

My new dyestuffs correspond to the following general formula: v I

, remarkably 'usual manner.

- InGermany September 27,

2 Claims. (Cl. 260-'173) 11, S. Patent 1,150,656 the new dyestuffs aredistinguished both in the direct dyeing and in the PATENT, OFFICE dyeingaftertreated with formaldehyde by a considerably clearer shade, anessentially better I neutral and alkaline 'dischargeability and by aimproved fastness to Washingv and boiling.

'I'heffollowing examples illustrate the 'invention, without, however,restricting it thereto, the parts being by weight: l

Example 1 26 parts of 1r-amino-4-oxalylaminobenzene-3- sulfonic acid aredissolved in 150 parts of water. to' aneutral solution, 35 parts ,ofhydrochloric acid 19.5 B. are added and the mixture is cooled to 0.;this is then diazotized in the usualfmanner with 6.9 parts of sodiumnitrite for 2 hours. Thecomplete diazotization is run into a solutionfof18.7 parts of 1-amino-2-ethoxynaphthalene in 800 parts ofwater and-12.8parts of sulfuric acid 60 Be. Thereupon the mixture is brought to a pHof 4.5 'to by adding 40 parts of anhydrous sodium acetate. The couplingliquor is rendered alkaline at 5 Cfwith' 69 parts of sodium hydroxideisolution 38 B. and diazotized 'with 13.3 parts of sodium nitrite and 120parts of hydrochloric .acid 19.5 B. in the The diaziotization 'pr'oductis separated by adding. salt, filtered off, pasted againwith'water andcoupled at 0 C. with a solution of 35.8 parts of 2-(3-aminobenzoylamino)-5-hydroXynaphthalene-7-sulf0nic' acid" in 69 parts of 2.20% ammoniasolutionand 133 parts of pyridine 100%. ,Th'paste of the disazodyestuff'is filtered ofl and again pasted with water and diazotizedat toC. with60partsof hydrochloric acid 19.5 B. and 6.9 parts of sodiumnitrite'for 4-'-5 hours andthereupon coupled with 6.9 parts ofresorcinol dissolved innwater containing i'parts of sodium carbonate.The complete trisazo dyestufi is. separated at '70?- C.

by:addin'g salt, and'filtered ofi. 'Ihe paste is saponified withf1'72parts of sodium: hydroxide solution 38 Beat-60C. for 20 minutes, Then II NH NET-000w:

the .mixture is acidified by hydrochloric acid, rendered alkaline againby adding sodium carbonate, separated by adding a little. salt, andfiltered off. The dyestufi thus obtained corresponds in the free stateto the following formula:

SOaH OC2H5 OH.. and yields very clear green shades which are both,aftertreated and in the direct dyeing, of an excellent neutral andalkaline dischargeability.

H is

HzN N=N N:

s 0.1: o 01H:

Example 2 ther diazotizing, coupling with resorcinol and saponifying ofthe dyestuff thus obtained is carried out as described in Example 1. Thenew dyestuff which corresponds in its free state to Y the followingformula:

SOaH- $03K 002115 OH yields bluish-green shades which are distinguishedin the direct andin the aftertreated dyeing byv a very good neutral andalkaline dischargeability.

Example 3 The azo dyestuff described in Example 1 and obtained fromdiazotized fl-amino-i-oxalylaminobenZene-B-suIfonic acid and1-a'mirio-2- eth'oxynaphthalene' is" further' diazotized as stated with13.3 parts ofsodium nitrite and by drochloric acid, filtered off andthe'diazo com pound, which is pasted again, is coupled at 0 C.-

' l NH.C 001%:

with 47.7 parts of 2-(3-aminobenzoyl-3- aminobenzoylamino) 5hydroxynaphthalene- I-sulfonicacid in 69 parts of a 20% ammonia solutionand 138 parts of 100% pyridine. Further diazotization, coupling withresorcinol and NH.COQI

s'aponification of the dyestufi, thus obtained, is carried out asdescribed in Example 2. The dyestuff thus obtainedcorresponds in itsfree state to the following formula: 1

Instead of 2- (3 'aminobenzoyl-3-aminobenzoylamino) -5hydroxynaphthalene '7-sulfonic acid, also the corresponding p-morp-paminobenzoylaminobenZoyl-compounds may be used in each instance.Dyestuffs are obtained which yield somewhat bluish-green shades beingvery well dischargeable both in the direct and in the aftertreateddyeing.

I claim:

1. Asnew products substantive polyazo dyestuffs of the general formula:

wherein AN=N stands forthe residue of a diazotizedp-phenylene-diamine-S-sulfonic acid X stands for one of the groupconsisting of hydrogen and the SO3H group, and 11. means one of thevalues 1 and 0, yielding clear green shades of good fastness propertiesand excellentneutral and alkaline dischargeability both in the'directdyeings and the dyeingsaftertreated with formaldehyde. 1

2. As a new product the subtantive polyazo dyestuif which corresponds inits free state to the formula:

and yields-very clear green shades of excellent neutral. and alkalinedischargeability both in the direct dyeing and the dyeing aftertreatedwith formaldehyde. r

l THEODOR KOLLMANN;

